Advances in Many-body Valence-bond Theory

Advances in Many-Body Valence-Bond Theory 

The area of valence-bond theory as advocated by Linus Pauling has come to be more widely accepted as encompassing interesting novel many-body characteristics, and several many-body techniques have been apparently successfully developed to greatly enhance the theory s computational amenability. 

The idea of valence structures goes back to classical chemistry. And indeed it was then at the heart of chemistry, though the theory was largely of a qualitative nature. There are both brief surveys [1,2] encompassing this history, as well as whole books on the subject [3]. 

But an alternative Molecular-Orbital (MO) approach eclipsed the VB approach, in so far as quantum-chemical research was concerned (say from the 1940s onward for a few decades). There were a variety of reasons for this, including perceived theoretical conceptual difficulties and supposed predictive failures - and perhaps most seriously the MO approach seemed much more computationally amenable. 

All this history is somewhat more fully discussed (from several points of view) in a couple review articles [2] as well as the first two chapters of [9] Valence-Bond Theory and Chemical Structure. These reviews describe through the period of this eclipse VB-theoretic work which was continued by a (prestigious or perhaps stubborn) minority of researchers (including Daudel, Hartmann, Simpson, Kotani, McWeeny, Lowdin, 

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Klein, D. J. Advances in Many-Body Valence-Bond Theory. In Pauling s Legacy Modern Modelling of the Chemical Bond, Maksid, Z. B., Orville-Thomas, W. J., Eds. Theoretical Computational Chemistry 9 Elsevier Amsterdam, 1999 pp 403-420. 

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